Catalyst component for polymerization of olefins

ABSTRACT

A titanium-containing catalyst component for polymerization of olefins which is prepared by reacting a magnesium hydrocarbyl oxide with a silicon compound having a hydrogen-silicon bond, contacting the reaction product with an electron donor compound, contacting the resulting contact product with an organoaluminum compound and further with a titanium compound.

DESCRIPTION OF THE INVENTION

1. Field of Technology

The present invention relates to a catalyst component for polymerizationof olefins. More particularly, the invention relates to (a) a catalystcomponent which provides olefin polymers having a high stereoregularityand a high bulk density in high yields, (b) an olefin polymerizationcatalyst system comprising the titanium halide-containing catalystcomponent and an organo metal cocatalyst, and (c) the process ofpolymerizing olefins in the presence of the catalyst system.

2. Background Technology

Heretofore, it has been known that a contact product of a halogen-freemagnesium compound and a titanium compound is useful as a catalystcomponent for the polymerization of olefins. However, it is low incatalytic performance, and attempts have been made for improvement. Suchattempts include a process in which Mg(OR)₂ is contacted with titaniumtetrahalide in the presence of a halogenated silane represented bySiX_(p) R_(4-p) (X=halogen, R=hydrocarbyl radical) or in the presence ofsaid halogenated silane and an electron donor compound (Japanese PatentLaid-open No. 98076/1977), a process in which a magnesium compoundhaving the Mg-O-R linkage is contacted with a halogenating agent such asa silicon compound represented by the formula X_(m) SiR_(n) (X and Rbeing as defined above) in the presence of an electron donor compound(Japanese Patent Laid-open No. 43094/1978), a process in which the solidreaction product of a halogenated aluminum, an organic compound havingthe Si-O bond, and magnesium alcoholate is contacted with a tetravalenttitanium compound having at least one halogen atom (U.S. Pat. No.4,242,479), a process in which the reaction product of a magnesiumcompound, titanium compound, and silicon compound is contacted with atleast one kind of halogenated aluminum compound (Japanese PatentLaid-open No. 155205/1981).

The catalyst components obtained according to the above-mentionedprocesses, however, are poor in catalytic activity and stereoregularityand provide polymers havlng a low bulk density. In addition to theabove-mentioned catalyst components, there is known one which isobtained by contacting a magnesium compound, an electron donor compound,a silicon compound having the Si-H bond, and a titanium halide compoundall together (Japanese Patent Laid-open No. 92009/1982). According tothis process, the magnesium compound is essentially a magnesium halideand the silicon compound and titanium halide are used simultaneously forcontacting. Therefore, the resulting product is not necessarilysatisfactory.

SUMMARY OF THE INVENTION

In order to produce from a halogen-free magnesium compound a catalystcomponent which can be made into a catalyst which exhibits highstereoregularity and high catalytic activity and provides olefinpolymers having a high bulk density, the present inventors carried outextensive researches, which led to the findings that the object can beachieved with a solid substance obtained by reacting a magnesiumhydrocarbyl oxide with a silicon compound having at least onehydrogen-silicon bond, contacting the reaction product with an electrondonor compound, contacting the resulting contact product with anorganoaluminum compound and finally contacting with a titanium compound.The present invention has been completed based on these findings.

The essence of this invention resides in a catalyst component forpolymerization of olefins which is prepared by reacting a magnesiumhydrocarbyl oxide with a silicon compound having at least onehydrogen-silicon bond, contacting the reaction product with an electrondonor compound, and contacting the resulting contact product with anorganoaluminum compound and further with a titanium compound.

RAW MATERIALS FOR CATALYST COMPONENT

The raw materials used for preparing the catalyst component of thisinvention are described below.

(A) Magnesium Alkoxide

The magnesium hydrocarbyl oxide used in this invention is represented bythe formula Mg(OR)(OR'), wherein R and R' are alkyl, alkenyl,cycloalkyl, aryl, or aralkyl groups having 1 to 20 carbon atoms,preferably 1 to 10 carbon atoms, and R and R' may be the same ordifferent.

These compounds include, for example, Mg(OCH₃)₂, Mg(OC₂ H₅)₂ (OCH₃)(OC₂H₅), Mg(Oi-C₃ H₇)₂, Mg(OC₃ H₇)₂, Mg(OC₄ H₉)₂, Mg(Oi-C₄ H₉)₂, Mg(OC₄H₉)(O-iC₄ H₉), Mg(OC₄ H₉)(Osec-C₄ H₉), Mg(OC₆ H₁₃)₂, Mg(OC₈ H₁₇)₂,Mg(OC₆ H₁₁)₂, Mg(OC₆ H₅)₂, Mg(OC₆ H₄ CH₃)₂, and Mg(OCH₂ C₆ H₅)₂.

These magnesium hydrocarbyl oxides should preferably be dried beforeuse, and more preferably be dried with heating under reduced pressure.These magnesium hydrocarbyl oxides may be obtained commercially or maybe synthesized according to the known methods.

These magnesium hydrocarbyl oxides may be contacted with an inorganic ororganic inert solid substance prior to use.

Suitable inorganic solid substances include metal compounds in the formof sulfate, hydroxide, carbonate, phosphate, or silicate. Examples ofsuch compounds include Mg(OH)₂, BaCO₃, and Ca₃ (PO₄)₂.

Suitable organic solid substances include low-molecular aromatichydrocarbons such as durene, anthracene, napthalene, and diphenyl. Theyalso include high-molecular compounds such as polyethylene,polypropylene, polyvinyl toluene, polystyrene, polymethyl methacrylate,polyamide, polyester, and polyvinyl chloride.

(B) Silicon Compound

The silicon compound used in this invention may be any compound havingthe hydrogen-silicon bond. It is represented by the formula H_(m) R_(n)SiX_(r), wherein R is (1) a hydrocarbon group, (2) R'O-(R' is ahydrocarbon group), (3) R² R³ N- (R² and R³ are hydrocarbon groups), or(4) R⁴ COO- (R⁴ is a hydrogen atom or hydrocarbon group); X is a halogenatom; and m is 1 to 3, 0≦r<4, and m+n+r=4. When n is greater than 1, Rmay be the same or different.

The hydrocarbon groups represented by R, R¹, R², R³, and R⁴ includealkyl, alkenyl, cycloalkyl, aryl, and aralkyl groups of carbon number 1to 16. The alkyl group includes, for example, methyl, ethyl, propyl,n-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, and n-decyl. Thealkenyl group includes, for example, vinyl, allyl, isopropenyl,propenyl, and butenyl. The cycloalkyl group includes, for example,cyclopentyl and cyclohexyl. The aryl group includes, for example,phenyl, tolyl, and xylyl. The aralkyl group includes, for example,benzyl, phenetyl, and phenylpropyl.

Preferable among them are lower alkyl groups such as methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, and t-butyl, and aryl groups suchas phenyl and tolyl.

X denotes halogen atoms such as chlorine, bromine, and iodine. Thepreferred halogen is chlorine.

The silicon compounds are exemplified by HSiC₃, H₂ SiCl₂, H₃ SiCl, HCH₃SiCl₂, HC₂ H₅ SiCl₂, H(t-C₄ H₉)SiCl₂, HC₆ H₅ SiCl₂, H(CH₃)₂ SiCl, H(i-C₃H₇)₂ SiCl, H₂ C₂ H₅ SiCl, H₂ (n-C₄ H₉)SiCl, H₂ (C₆ H₄ CH₃)SiCl,HSi(CH₃)₃, HSiCH₃ (OCH₃)₂, HSiCH₃ (OC₂ H₅)₂, HSi(OCH₃)₃, (C₂ H₅)₂ SiH₂,HSi(CH₃)₂ (OC₂ H₅), HSi(CH₃)₂ [N(CH₃)₂ ], HSiCH₃ (C₂ H₅)₂, HSiC₂ H₅ (OC₂H₅)₂, HSiCH₃ [N(CH₃)₂ ]₂, C₆ H₅ SiH₃, HSi(C₂ H₅)₃, HSi(OC₂ H₅)₃,HSi(CH₃)₂ [N(C₂ H₅)₂ ], HSi[ N(CH₃)₂ ]₃, C₆ H₅ CH₃ SiH₂, C₆ H₅ (CH₃)₂SiH, (n-C₃ H₇)₃ SiH, HSiCl(C₆ H₅)₂, H₂ Si(C₆ H₅)₂, HSi(C₆ H₅)₂ CH₃,(n-C₅ H₁₁ O)₃ SiH, HSi(C₆ H₅)₃, and (n-C₅ H₁₁)₃ SiH. Another example ofthe compounds not covered by the above formula include (ClCH₂ CH₂ O)₂-CH₃ SiH, HSi(OCH₂ CH₂ Cl)₃, [H(CH₃)₂ Si]₂ O, [H(CH₃)₂ Si]₂ NH, (CH₃)₃SiOSi(CH₃)₂ H, [H(CH₃)₂ Si]₂ C₆ H₄, [H(CH₃)₂ SiO]₂ Si(CH₃)₂, [(CH₃)₃SiO]₂ SiHCH₃, [(CH₃)₃ SiO]₃ SiH, and ##STR1##

Preferable among these halogenated silicon compounds are those wich arerepresented by the formula in which R is a hydrocarbon, n is 0 to 2, andr is 1 to 3. They are HSiCl₃, H₂ SiCl₂, H₃ SiCl, HCH₃ SiCl₂, HC₂ H₅SiCl₂, H(t-C₄ H₉)SiCl₂, HC₆ H₅ SiCl₂, H(CH₃₂ SiCl, H(i-C₃ H₇)₂ SiCl, H₂C₂ H₅ SiCl, H₂ (n-C₄ H₉)SiCl, H₂ (C₆ H₄ CH₃)SiCl, and HSiCl(C₆ H₅)₂.Most preferable among them are HSiCl₃, HCH₃ SiCl₂, and H(CH₃)₂ SiCl.Especially preferred among the silicon compounds is HSiCl₃.

(C) Electron Donor Compound

The electron donor compound used in this invention includes carboxylicacids, carboxylic anhydrides, carboxylic esters, carboxylic acidhalides, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes,alcoholates, phosphoamides, thioethers, thioesters, and carbonic esters,andphosphrus, arsenic, and antimony compounds in which these atoms arebonded to an organic group through a carbon or oxygen. Preferable amongthem are carboxylic esters, carboxylic anhydrides, carboxylic acidhalides, alcohol, and ethers.

Examples of carboxylic esters include butyl formate, ethyl acetate,butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl isobutyrate,methyl methacrylate, diethyl maleate, diethyl tartrate, ethylcyclohexanecarbonate, ethyl benzoate, ethyl p-methoxybenzoate, methylp-methylbenzoate, ethyl p-tert-butylbenzoate, dibutyl phthalate, diallylphthalate, and ethyl alpha-naphthoate. They are not limitative.Preferable among them are alkyl esters of aromatic carboxylic acid,particularly C₁₋₈ alkyl esters of benzoic acid or nucleus-substitutedbenzoic acid such as p-methylbenzoic acid and p-methoxy benzoic acid.

Examples of the carboxylic anhydride include aliphatic monocarboxylicanhydrides such as acetic anhydride, propionic anhydride, butyricanhydride, valeric anhydride, and caproic anhydride; aliphaticolefinmonocarboxylic anhydride such as acrylic anhydride, crotonicanhydride, and methacrylic anhydride; alicyclic carboxylic anhydridessuch as cyclohexanemonocarboxylic anhydride, cyclohexenemonocarboxylicanhydride, cis-1,2-cyclohexanedicarboxylic anhydride, andcis-4-cyclohexene-1,2-dicarboxylic anhydride; aromatic monocarboxylicanhydrides such as benzoic anhydride, p-toluylic anhydride,p-ethylbenzoic anhydride, and p-methoxybenzoic anhydride; and aromaticdicarboxylic anhydrides such as phthalic anhydride.

Examples of the carboxylic acid halides include aliphatic monocarboxylicacid halides (acid chlorides such as acetyl chloride, propionylchloride, n-butyl chloride; and acid bromides such as acetyl bromide andn-butyl bromide; and acid iodides such as acetyl iodide and n-butyliodide), aliphatic monoolefincarboxylic acid halides (acid chloridessuch as acryl chloride, crotonyl chloride, and methacryl chloride; acidbromides such as acryl bromide and methacryl bromide; and acid iodidessuch as acryl iodide and methacryl iodide), alicyclic carboxylic acidhalides (cyclohexane-carboxylic acid chloride,cis-4-methylcyclohexanecarboxylic acid chloride, 1-cyclohexenecarboxylicacid chloride, cyclohexanecarboxylic acid bromide, andcis-4-methylhexenecarboxylic acid bromide), aromatic monocarboxylic acidhalides (acid chlorides such as benzoyl chloride, p-toluic acidchloride, p-ethylbenzoic acid chloride, and p-methoxybenzoic acidchloride; acid bromides such as benzoyl bromide; and acid iodides suchas benzoyl iodide), and aromatic dicarboxylic acid halides such asphthalic acid dichloride.

The alcohols are represented by the formula ROH, wherein R is an alkyl,alkenyl, cycloalkyl, aryl, or aralkyl group of carbon number 1 to 12.Examples of the alcohols include methanol, ethanol, propanol,isopropanol, butanol, isobutanol, pentanol, hexanol, octanol,2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol,cresol, xylenol, ethylphenol, isopropylphenol, p-t-butylphenol,n-octylphenol, and naphthol.

The ethers are represented by the formula ROR', wherein R and R' arealkyl, alkenyl, cycloalkyl, aryl, or aralkyl groups of carbon number 1to 12, and R and R' may be the same or different. Examples of the ethersinclude diethyl ether, diisopropyl ether, dibutyl ether, diisobutylether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethylallyl ether, butyl allyl ether, diphenyl ether, anisole, and ethylphenyl ether.

(D) Organoaluminum Compound

The organoaluminum compound (component D) used in this invention is onewhich is represented by the formula R_(n) AlX_(3-n), wherein R is analkyl group or aryl group, X is a halogen atom, alkoxy group, orhydrogen atom, n is an arbitrary number in the range of 1≦n≦3. Preferredones are alkyl aluminum compounds and a mixture thereof or complexthereof having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms,such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkylaluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminummonoalkoxide, and dialkyl aluminum monohydride. Examples of suchcompounds include trialkyl aluminum such as trimethyl aluminum, triethylaluminum, tripropyl aluminum, triisobutyl aluminum, and trihexylaluminum; dialkyl aluminum monohalide such as dimethyl aluminumchloride, diethyl aluminum iodide, and diisobutyl aluminum chloride;monoalkyl aluminum dihalide such as methyl aluminum dichloride, ethylaluminum dichloride, methyl aluminum dibromide, ethyl aluminumdibromide, ethyl aluminum diiodide, and isobutyl aluminum dichloride;alkyl aluminum sesquihalide such as ethyl aluminum sesquichloride;dialkyl aluminum monoalkoxide such as dimethyl aluminum methoxide,diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminumethoxide, diisobutyl aluminum ethoxide, and diisobutyl aluminumphenoxide; and dialkyl aluminum hydride such as dimethyl aluminumhydride, diethyl aluminum hydride, dipropyl aluminum hydride, anddiisobutyl aluminum hydride.

Particularly preferable among them are triethyl aluminum, diethyaluminumchloride, ethylaluminum sesquichloride, and ethylaluminum dichloride.

(E) Titanium Compound

The titanium compound used in this invention includes divalent,trivalent, and tetravalent titanium compounds. They are exemplified bytitanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium,dichlorodibutoxytitanium, dichlorodiphenoxytitanium,chlorotiethoxytitanium, chlorotributoxytitanium, tetrabutoxytitanium,and titanium trichloride. Preferable among them are tetravalent titaniumhalides such as titanium tetrachloride, trichloroethoxytitanium,dichlorobutoxytitanium, and dichlorodiphenoxytitanium, and mostpreferable is titanium tetrachloride.

Preparation of Catalyst Component

The catalyst component of this invention is prepared by reacting amagnesium hydrocarbyl oxide (component A) with a silicon compound(component B), contacting the reaction product with an electron donorcompound containing at least one H-Si bond (component C), and contactingthe resulting contact product with an organoaluminum compound (componentD) and further with a titanium compound (component E). The process isdescribed below.

(1) Reaction of Magnesium Alkoxide with Silicon Compound

The reaction of a magnesium hydrocarbyl oxide (component A) with asilicon compound containing at least one H-Si bond (component B) isaccomplished by contacting the two components with each other. Thecontacting can be accomplished by mixing/stirring or mechanicallycopulverizing the two compounds in the presence or absence of ahydrocarbon. Preferably, the two components should be mixed and stirredin a hydrocarbon.

The preferred hydrocarbon is a saturated aliphatic, saturated alicyclic,or aromatic hydrocarbon of carbon number 6 to 12 such as hexane,heptane, octane, cyclohexane, benzene, toluene, and xylene.

One mol of component A is contacted with 0.5 to 10 mol, preferably 1 to50 mol of component B. Usually, the contacting is performed at 0° to200° C. for 0.5 to 100 hours. More than one kind each of component A andcomponent B may be used.

The hydrocarbon may be used in any amount; but it should preferably beless than 100 ml for 1 g of component A.

The quantity of silicon atom in the reaction product, which is insolublein an inert solvent, particularly n-hexane or n-heptane, at 65° C., ismore than 8 wt %.

The contact product of component A and component B is separated from thereaction system, and is used for the subsequent contacting. Ifnecessary, it may be washed with an inert hydrocarbon such as one whichis used in the contacting of component A and component B, prior to thesubsequent contacting. This washing may be carried out with heating.

(2) Contacting with Electron Donor Compound

The contacting of the reaction product obtained in the above step (1)with an electron donor compound (component C) may be accomplished bymixing and stirring them together in the presence or absence of an inerthydrocarbon, or by mechanically copulverizing them. The inerthydrocarbon includes hexane, heptane, octane, cyclohexane, benzene,toluene, and xylene.

The contacting by mechanical copulverization should be carried out at 0° to lO0° C. for 0.1 to 100 hours. The contacting by mere stirringshould be carried out at 0° to 150° C. for 0.5 to 10 hours.

Component C is used in an amount of 0.01 to 10 gram mol, particularly0.05 to 1 gram mol, for 1 gram atom of magnesium in the reaction productof magnesium alkoxide and silicon compound.

(3) Contacting with Organoaluminum Compound

The contact product (contact product 1) obtained in the above step (2)is subsequently contacted with an organoaluminum compound (component D).Before being contacted with component D, the contact product 1 may bewashed with a proper cleaning agent such as the above-mentioned inerthydrocarbon. The contact product 1 and component D may be contacted witheach other as such; but it is preferable that they are mixed and stirredin a hydrocarbon. The hydrocarbon includes hexane, heptane, octane,cyclohexane, benzene, toluene, and xylene.

Component D is used in an amount of 0.1 to 20 mol, preferably 0.5 to 5mol, for 1 mol of component C in the contact product 1.

The contacting in a hydrocarbon should be carried out at 0° to lOO° C.for 0.1 to 15 hours, and preferably at 10° to 70° C. for 0.5 to 5 hours.

More than one kind of component D may be used simultaneously; and thecontacting with component D may be carried out more than once.

(4) Contacting with Titanium Compound

The contact product (contact product 2) obtained in the above step (3)is then contacted with a titanium compound (component E). Prior tocontacting with component E, the contact product 2 may be washed with aproper cleaning agent such as the above-mentioned inert hydrocarbon.

The contact product 2 and component E may be contacted with each otheras such; but it is preferable that they are mixed and stirred in ahydrocarbon. The hydrocarbon includes hexane, heptane, octane,cyclohexane, benzene, toluene, and xylene.

Component E is used in an amount more than 0.1 gram mol, preferably 1 to50 gram mol, for 1 gram atom of magnesium in the contact product 2.

The contacting should be carried out at 0° to 200° C. for 0.5 to 20hours, and preferably at 60° to 150° C. for 1 to 5 hours.

The contacting with component E should preferably be carried out morethan once. Where the previous contacting has been carried out in ahydrocarbon, the contact product should be separated from thehydrocarbon prior to the subsequent contacting.

Where the contacting with component E is carried out more than once, itis recommended that the contact product 2 be contacted with ahalogenated hydrocarbon or a halide of an element selected from thegroup consisting of the elements of Groups IIa, IVa, and Va of theperiodic table of elements at the interval of the contacting. This willimprove the catalytic performance of the resulting catalyst component.

The halogenated hydrocarbon used in this step is a mono- and polyhalogensubstitute of saturated or unsaturated aliphatic, alicyclic, or aromatichydrocarbon having 1 to 12 carbon atoms. Examples of aliphatic compoundsinclude methyl chloride, methyl bromide, methyl iodide, methylenechloride, methylene bromide, methylene iodide, chloroform, bromoform,iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide,ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane,1,2-dibromoethane, 1,2-diiodoethane, methylchloroform, methylbromoform,methyliodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene,1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane,hexabromoethane, n-propylchloride, 1,2-dichloropropane,hexachloropropylene, octachloropropane, decabromobutane, and chlorinatedparaffin. Examples of alicyclic compound include chlorocyclopropane,tetrachlorocyclopentane, hexachloropentadiene, andhexachlorocyclohexane. Examples of aromatic compounds includechlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene,hexachlorobenzene, hexabromobenzene, benzotrichloride, andp-chlorobenzotrichloride. These compounds may be used individually or incombination with one another.

The halide of an element selected from the elements in Groups IIIa, IVa,and Va of the periodic table of elements (referred to as metal halidehereinafter) includes, for example, halides, fluorides, bromides, andiodides ob B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. Preferableamong them are BCl₃, BI₃, AlCl₃, AlBr₃, AlI₃, GaCl₃, GaBr₃, InCl₃,TiCl₃, SiCl₄, SnCl₄, SbCl₅, and SbF₅.

The contacting with a halogenated hydrocarbon (component F) isaccomplished by contacting the solids (which has been separated from thecontact product with component E) with component F.

The solids and component F may be contacted with each other as such orin a hydrocarbon. The contacting may be accomplished by mechanicalcopulverizing or mixing and stirring.

Component F is used in an amount of more than 0.1 mol, preferably 0.5 to200 mol, for 1 gram atom of magnesium in the solid. The contacting isaccomplished at 0° to 200° C. for 0.1 to 15 hours, preferably 25° to 90°C. for 0.5 to 5 hours.

The solid may be contacted with a metal halide (component G) in the samemanner as used for contacting the solid with component F. Component G isused in an amount more than 0.1 mol, preferably 0.5 to 150 mol, for 1gram atom of magnesium in the solid. The contacting is accomplished at0° to 200° C. for 0.1 to 15 hours, preferably 25° to 90° C. for 0.5 to 5hours.

The solid substance obtained as mentioned above is washed, if required,with an inert hydrocarbon such as hexane, heptane, octane, cyclohexane,benzene, toluene, and xylene, followed by drying, whereby there isobtained the catalyst component of this invention.

The catalyst component of this invention is powder having a specificsurface area of 50 to 650 m² /g as measured by BET method at theadsorption temperature of liquid nitrogen, a pore volume of 0.05 to 0.40cc/g, and a narrow particle size distribution.

Catalyst for Polymerization of Olefin

The catalyst component of this invention is combined with anorganoaluminum compound to be made into a catalyst forhomopolymerization of an olefin or for copolymerization of an olefin andother olefin.

Organoaluminum Compound

The organoaluminum compound to be combined with the catalyst componentmay be the same one as used in the preparation of the catalystcomponent.

Preferable among them is trialkyl aluminum, particularly triethylaluminum and triisobutyl aluminum. The trialkyl aluminum can be used incombination with the other organoaluminum compound such as commerciallyavailable diethyl aluminum chloride, ethyl aluminum dichloride, ethylaluminum sesquichloride, diethyl aluminum ethoxide, and diethyl aluminumhydride, and a mixture or complex thereof.

In addition, the organoaluminum compound may be used alone or incombination with an electron donor compound. Any electron donor compoundused in the preparation of the catalyst component of this invention maybe used. Preferable ones are carboxylic acid esters, alcohols, ethers,and ketones. The electron donor compound may be used when anorganoaluminum compound is used in combination with the catalystcomponent, or may be used after being contacted with an organoaluminumbeforehand.

The organoaluminum compound is used in an amount of 1 to 2000 gram mol,preferably 20 to 500 gram mol, for 1 gram atom of titanium in thecatalyst component.

The ratio of the organoaluminum compound to the electron donor compoundis such that aluminum in the organoaluminum compound is 0.1 to 40 gramatom, preferably 1 to 25 gram atom, for 1 mol of the electron donorcompound.

Polymerization of Olefin

The catalyst composed of the catalyst component prepared as mentionedabove and an organoaluminum compound (and an electron donor compound) isuseful as a catalyst for homopolymerization of monoolefin orcopolymerization of monoolefin and other monoolefin or diolefin. Itexhibits outstanding performance as a catalyst for homopolymerization ofan alpha-olefin of carbon number 3 to 6, such as propylene, 1-butene,4-methyl-1-pentene, and 1-hexene, or random or block copolymerization ofthe above-mentioned alpha-olefins with one another or with ethylene; andfor homopolymerization of ethylene or random or block copolymerizationof ethylene with an alpha-olefin of carbon number 3 to 10, such aspropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene.

The polymerization may be performed either in gas phase or liquid phase.The liquid phase polymerization may be accomplished in an inerthydrocarbon such as n-butane, isobutane, n-pentane, isopentane, hexane,heptane, octane, cyclohexane, benzene, toluene, and xylene, or in theliquid monomer. The polymerization temperature is usually -80° C. to+150° C., preferably 40° C. to 120° C. The polymerization pressure is 1to 60 atm. The molecular weight modification of the resulting polymer isaccomplished in the presence of hydrogen or other known molecular weightmodifiers. In the copolymerization of olefin, the quantity of otherolefin to be copolymerized is usually less than 30 wt %, particularly0.5 to 15 wt %, based on the olefin. The polymerization with thecatalyst system of this invention may be performed continuously orbatchwise under the commonly used conditions. The copolymerization maybe accomplished in one step or in two or more steps.

Effect of Invention

The catalyst component of this invention is useful for the production ofpolyolefins, particularly isotactic polypropylene, ethylene-propylenerandom copolymer, and ethylene-propylene block copolymer.

The polymerization catalyst made from the catalyst component of thisinvention exhibits a high catalytic activity and stereoregularities andkeeps its high activity for a long time during polymerization. Itprovides polymer powder having a high bulk density and flowability.

EXAMPLES

The invention is described in more detail with reference to thefollowing examples and application examples. The scope of this inventionis not limited by these examples. Percent (%) in the examples andapplication examples means wt %, unless otherwise indicated.

The specific surface area (S.A.) and pore volume (P.V.) of the catalystcomponent were measured by using SORPTOMATIC, Model 1810, made by CARLOERBA.

The catalytic activity Kc is the quantity (g) of polymer formed per 1 gof catalyst, and Kt is the quantity (kg) of polymer formed per 1 g oftitanium in the catalyst.

The heptane insoluble (referred to as HI hereinafter) which indicatesthe ratio of crystalline fractions in the polymer is the quantity ofresidues which remain after extraction for 6 hours with boilingn-heptane in a Soxhlet apparatus of improved type.

The melt flow rate (MFR) and melt index (MI) were measured according toASTM-D1238. The bulk density was measured according to ASTM-D1895-69,Method A.

EXAMPLE 1 Contacting of Magnesium Diethoxide with Trichlorosilane

Into a 2-liter glass reactor equipped with a reflux condenser, droppingfunnel, and stirrer and replaced with nitrogen were charged 120 g (1.05mol) of commercial magnesium diethoxide and 680 ml of n-heptane. Withstirring at room temperature, a mixture of 356 g (2.63 mol) oftrichlorosilane and 250 ml of n-heptane was added dropwise from thedropping funnel over 45 minutes. Stirring was continued for 6 hours at70° C. During the reaction, a gas composed mainly of ethylene and ethylchloride formed. The resulting solids were filtered off at 70° C. andthen washed by stirring in 600 ml of n-hexane at 65° C. for 10 minutes.The supernatant liquid was removed by decantation. Washing with n-hexanewas repeated 4 times, and the solids were dried at 60° C. for 1 hourunder reduced pressure. Thus there was obtained 164 g of solid component(I). This solid component was found to contain 12.9% of magnesium, 14.1%of silicon, and 45.7% of chlorine, and to have a specific surface areaof 31 m² /g and a pore volume of 0.08 cc/g.

Contacting with Benzoic Anhydride

18 g of the solid component (I) was placed in a 300-ml stainless steel(SUS316) mill pot containing 100 pieces of stainless steel (SUS316)balls, 12 mm in diameter, under the nitrogen atmosphere. Then 4.5 g ofbenzoic anhydride was added to the mill pot. The mill pot was mounted ona shaker and shaken for 1 hour for crushing. Thus there was obtained asolid component (II).

Contacting with Triethyl Aluminum

7.0 g of the solid component (II) was placed in a 200-ml glass reactorequipped with a stirrer and dropping funnel under the nitrogenatmosphere. Then 60 ml of n-heptane was added, followed by stirring tomake slurry. Then a mixture of 1.0 ml of triethyl aluminum and 30 ml ofn-heptane was added dropwise at room temperature over 15 minutes.Reaction was continued at 50° C. for 1 hour. The resulting solidsubstance was filtered off at 50° C., followed by washing four timeswith 90 ml portions of n-hexane at 50° C. Thus there was obtained asolid component (III) in the form of slurry.

Contacting with Titanium Tetrachloride

To the solid component (III) were added 40 ml of toluene and 60 ml oftitanium tetrachloride, followed by stirring at 90° C. for 2 hours. Theresulting solid substance was filtered off at 90° C. and washed 7 timeswith 90 ml portions of n-hexane at room temperature. After drying atroom temperature for 1 hour under reduced pressure, there was obtained5.4 g of catalyst component containing 2.6% of titanium, 17.2% ofmagnesium, 57.2% of chlorine, and 3.0% of silicon. The specific surfacearea was 318 m² /g and the pore volume was 0.28 cc/g.

EXAMPLE 2

8.5 g of the solid component (I) obtained in Example 1 was placed in a200-ml glass reactor equipped with a stirrer under the nitrogenatmosphere. Then 90 ml of n-heptane and 3.0 g of benzoyl chloride wereadded, followed by reaction at 70° C. for 2 hours. The reaction productwas washed 3 times with 90 ml portions of n-heptane at 65° C. Thus therewas obtained the solid component (II). To this solid component (II) wereadded 90 ml of n-heptane and 2.2 ml of triethyl aluminum, followed byreaction at 50° C. for 1 hour. The reaction product was washed 5 timeswith 90 ml portions of n-heptane to give the solid component (III) inthe form of slurry. This solid component (III) was contacted withtitanium tetrachloride and treated in the same way as in Example 1.There was obtained a catalyst component having the composition as shownin Table 1.

EXAMPLE 3

The solid component (III) obtained in Example 1 was placed in a 200-mlglass reactor equipped with a stirrer under the nitrogen atmosphere.Then 40 ml of toluene and 60 ml of titanium tetrachloride were added,followed by stirring at 90° C. for 2 hours. After removal of thesupernatant liquid by decantation, the reaction product was washed 4times with 90 ml portions of toluene at 60° C. Then 40 ml of toluene and60 ml of titanium tetrachloride were added again, followed by stirringat 90° C. for 2 hours.

The resulting solid substance was filtered off at 90° C. and washed 7times with 90 ml portions of n-hexane at room temperature, followed bydrying for 1 hour at room temperature under reduced pressure. Thus therewas obtained a catalyst component having the composition as shown inTable 1.

EXAMPLE 4

A catalyst component was prepared in the same way as in Example 3 bycontacting the solid component (III) obtained in Example 2 with titaniumtetrachloride twice. The composition of the catalyst component is shownin Table 1.

EXAMPLE 5

The solid component (II) was obtained in the same way as in Example 1,except that benzoic anhydride was replaced by ethyl benzoate. The solidcomponent (II) was contacted with triethyl aluminum in the same way asin Example 1 to give the solid component (III).

A catalyst component was prepared in the same way as in Example 3 bycontacting this solid component (III) with titanium tetrachloride twice.The composition of the catalyst component is shown in Table 1.

EXAMPLE 6

The solid component (II) was obtained in the same way as in Example 1,except that benzoic anhydride was replaced by 3.0 g of p-cresol and 4.5ml of ethyl benzoate. The solid component (II) was contacted withtriethyl aluminum in the same way as in Example 1 to give the solidcomponent (III).

A catalyst component was prepared in the same way as in Example 3 bycontacting this solid component (III) with titanium tetrachloride twice.The composition of the catalyst component is shown in Table 1.

EXAMPLE 7

The solid component (III) was obtained in the same way as in Example 1by contacting the solid component (II) obtained in Example 1 with ethylaluminum dichloride in place of triethyl aluminum. This solid component(III) was then contacted with titanium tetrachloride twice in the sameway as in Example 3 to give a catalyst component. The composition of thecatalyst component is shown in Table 1.

EXAMPLE 8

The solid component (III) was obtained in the same way as in Example 2by contacting the solid component (II) obtained in Example 2 withdiethyl aluminum chloride in place of triethyl aluminum. This solidcomponent (III) was then contacted with titanium tetrachloride twice inthe same way as in Example 3 to give a catalyst component. Thecomposition of the catalyst component is shown in Table 1.

EXAMPLE 9

The solid component (III) was prepared in the same way as in Example 1,except that trichlorosile was replaced by methyldichlorosilane. Thissolid component (III) was contacted with titanium tetrachloride twice inthe same way as in Example 3 to give a catalyst component having thecomposition as shown in Table 1.

EXAMPLE 10

The solid component (I) was prepared in the same way as in Example 1,except that trichlorosilane was replaced by methyldichlorosilane. Thesolid component (II) was prepared in the same way as in Example 2 bycontacting with benzoyl chloride. The solid component (III) was preparedby contacting with diethyl aluminum chloride in the same way as inExample 8.

This solid component (III) was contacted with titanium tetrachloridetwice in the same way as in Example 3 to give a catalyst componenthaving the composition as shown in Table 1.

EXAMPLE 11

To the solid component (III) obtained in Example 7 were added 40 ml oftoluene and 60 ml of titanium tetrachloride, followed by stirring at 90°C. for 2 hours. After removal of the supernatant liquid by decantation,80 ml of toluene and 6.2 g of hexachloroethane were added, followed byreaction at 60° C. for 1 hour. After washing 4 times with 90 ml portionsof toluene at 60° C., 40 ml of toluene and 60 ml of titaniumtetrachloride were added again, followed by stirring at 90° C. for 2hours.

The resulting solid substance was filtered off at 90° C. and washed 7times with 90 ml portions of n-hexane at room temperature, followed bydrying for 1 hour at room temperature under reduced pressure. Thus therewas obtained a catalyst component having the composition as shown inTable 1.

EXAMPLES 12 and 13

The solid component (III) obtained in Example 2 was placed in a 200-mlglass reactor equipped with a stirrer under the nitrogen atmosphere.Then 40 ml of toluene and 60 ml of titanium tetrachloride were added,followed by stirring at 90° C. for 2 hours. After removal of thesupernatant liquid by decantation, 85 ml of toluene and 6.3 g of silicontetrachloride (Example 12) or 5.2 g of tin tetrachloride (Example 13)were added, followed by stirring at 60° C. for 1 hour. The reactionproduct was washed 4 times with 90 ml portions of toluene at 60° C. Then40 ml of toluene and 60 ml of titanium tetrachloride were added,followed by stirring at 90° C. for 2 hours. The resulting solidsubstance was filtered off at 90° C. and washed 7 times with 90 mlportions of n-hexane at room temperature, followed by drying for 1 hourat room temperature under reduced pressure. Thus there was obtained acatalyst component having the composition as shown in Table 1.

Comparative Example 1

Into the same mill pot as used in Example 1 were charged under thenitrogen atmosphere 31.5 g of commercial magnesium diethoxide and 10.0 gof benzoic anhydride. The mill pot was shaken on a shaker for 15 hours.

5.0 g of the resulting ground solid was placed in a 500-ml glasscontainer equipped with a stirrer, and 330 ml of n-heptane was added andthen 9 ml of titanium tetrachloride was added dropwise over 15 minutes.Further, 35 ml of trichlorosilane was added dropwise in the same way,followed by stirring at 90° C. for 2 hours.

The resulting solid substance was filtered off at 90° C. and washed 6times with 150 ml portions of n-hexane at room temperature. The solidsubstance was dried at room temperature for 1 hour under reducedpressure. Table 1 shows the compositions of the resulting catalystcomponent.

Comparative Example 2

A catalyst component having the composition as shown in Table 1 wasprepared in the same way as in Comparative Example 1, except thatbenzoic anhydride was replaced by 7.5 ml of ethyl benzoate.

                  TABLE 1                                                         ______________________________________                                                Silicon Compound-                                                             treated Solid                                                                             Catalyst Component                                                Composition (%)                                                                           Composition (%)                                                   Mg   Si      Cl     Mg    Ti  Si   Cl                                 ______________________________________                                        Example                                                                       1         12.9   14.2    45.7 17.2  2.6 3.0  57.2                             2         12.9   14.1    45.7 16.8  2.5 3.4  56.8                             3         12.9   14.1    45.7 17.4  2.4 4.2  58.3                             4         12.9   14.1    45.7 17.6  2.5 3.8  57.2                             5         12.9   14.1    45.7 17.2  2.2 3.5  57.1                             6         12.9   14.1    45.7 17.1  2.6 3.7  56.8                             7         12.9   14.1    45.7 17.4  2.1 3.2  57.1                             8         12.9   14.1    45.7 17.2  2.2 3.8  57.6                             9         12.8   14.2    48.3 17.3  2.5 3.3  57.0                             10        12.8   14.2    48.3 18.1  2.3 3.4  56.9                             11        12.9   14.1    45.7 17.6  2.1 3.6  57.2                             12        12.9   14.1    45.7 16.9  2.0 3.5  56.9                             Comparative                                                                   Example                                                                       1         --     --      --   15.2  5.3 0.6  44.1                             2         --     --      --   14.3  5.9 0.6  42.6                             ______________________________________                                    

Application Example 1 Polymerization of Propylene

19.3 mg of catalyst component obtained in Example 1, 2.6 ml of triethylaluminum (abbreviated as TEAL hereinafter) solution in n-heptane, and0.14 ml of ethyl p-methoxybenzoate were mixed. After standing for 5minutes, the mixture was added to a 1.5-liter stainless steel (SUS 32)autoclave equipped with a stirrer under the nitrogen atmosphere. (Then-heptane solution of TEAL contains 1 mol of TEAL in 1 liter ofn-heptane, and 2.6 ml of the solution corresponds to 250 gram atom ofaluminum for 1 gram atom of titanium in the catalyst component. 0.14 mlof ethyl p-methoxybenzoate corresponds to 0.33 mol for 1 gram atom ofaluminum in TEAL.) Then, 0.6 liter of hydrogen as the molecular weightmodifier and 0.8 liter of liquefied propylene were forced into theautoclave. The reaction system was heated to 70° C., and thepolymerization of propylene was carried out for 1 hour. After thepolymerization was complete, unreacted propylene was purged. Thus therewas obtained 261 g of white polypropylene powder having an HI of 94.0%(heptane insolubles indicating the crystalline fraction in the polymer),an MFR of 2.8 (melt flow rate), and a bulk density of 0.38 g/cm³.Kc=13,500 [quantity (g) of polymer formed per 1 g of catalyst]Kt=519[quantity (kg) of polymer formed per 1 g of Ti in the catalyst]

Application Examples 2 to 15

Polymerization of propylene was carried out in the same way as inApplication Example 1, except that the catalyst component obtained inExample 1 was replaced by those which were obtained in Examples 2 to 13and Comparative Examples 1 and 2. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Appli-                         MFR   Bulk  density                            cation Catalyst   Kc      Kt   HI    (g/10 (g/                                Example                                                                              Component  (g)     (kg) (%)   min)  cm.sup.3)                          ______________________________________                                        1      Example 1  13,500  519  94.8  2.8   0.38                               2      Example 2  12,600  504  95.2  3.2   0.38                               3      Example 3  14,800  617  95.2  3.1   0.39                               4      Example 4  14,500  580  95.5  2.7   0.39                               5      Example 5  15,400  700  95.0  2.6   0.39                               6      Example 6  16,200  623  95.5  2.4   0.39                               7      Example 7  14,000  667  95.9  2.2   0.38                               8      Example 8  14,800  673  96.0  2.2   0.39                               9      Example 9  14,000  560  95.4  2.5   0.39                               10     Example 10 13,800  600  95.5  2.1   0.38                               11     Example 11 15,500  738  95.0  2.6   0.39                               12     Example 12 15,800  790  95.6  2.4   0.39                               13     Example 13 15,600  650  95.3  2.9   0.39                               14     Comparative                                                                                480    9   86.7  --    --                                        Example 1                                                              15     Comparative                                                                                600    10  85.1  --    --                                        Example 2                                                              ______________________________________                                    

What is claimed is:
 1. A catalyst component for the polymerization ofolefins obtained by (1) reacting (A) Mg(OR)(OR') with (B) a siliconcompound having at least one silicon-hydrogen bond, (2) contacting thereaction product with (C) an electron donor compound, (3) contacting theproduct from step (2) with an organoaluminum compound, and (4)contacting the step (3) product with a titanium compound, wherein R andR' are radicals selected from alkyl, alkenyl, cycloalkyl, aryl andaralkyl radicals and R and R' may be the same or different.
 2. Thecatalyst component of claim 1 wherein the titanium compound is selectedfrom divalent, trivalent or tetravalent titanium halides, alkoxytitanium compounds and haloalkoxy titanium compounds.
 3. The catalystcomponent of claim 2 wherein the titanium compound is titaniumtetrachloride.
 4. The catalyst component of claim 1 wherein the electrondonors are selected from carboxylic acid esters, carboxylic acid andhydrides, carboxylic acid halides, alcohols and ethers.
 5. The catalystcomponent of claim 4 wherein the electron donor is selected from benzoicanhydride, benzoyl chloride, ethyl benzoate, and p-cresol.
 6. Thecatalyst component of claim 1 wherein the silicon compound istrichlorosilane.
 7. The catalyst component of claim 1 wherein R and R'are alkyl radicals having from 1 to 8 carbon atoms.
 8. The catalystcomponent of claim 7 wherein R and R' are ethyl.
 9. The catalystcomponent of claim 1 wherein the organoaluminum compound is one oftriethylaluminum, diethylaluminum chloride, ethylaluminum sesquichlorideand ethylaluminum dichloride.
 10. The catalyst component of claim 1wherein the step (3) product is contacted with the titanium compound twoor more times.
 11. The catalyst component of claim 10 wherein between atleast one of a multiple titanium compound contacts, contacting thetitanium compound contacted solid is treated with a halogenatedhydrocarbon.
 12. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 1 and an organoaluminumcocatalyst.
 13. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 2 and an organoaluminumcocatalyst.
 14. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 3 and an organoaluminumcocatalyst.
 15. A catalyst system for the polymerization ofalpha-olefins comprising the catalyst component of claim 4 and anorganoaluminum cocatalyst.
 16. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 5 and anorganoaluminum cocatalyst.
 17. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 6 and anorganoaluminum cocatalyst.
 18. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 7 and anorganoaluminum cocatalyst.
 19. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 8 and anorganoaluminum cocatalyst.
 20. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 9 and anorganoaluminum cocatalyst.
 21. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 10 and anorganoaluminum cocatalyst.
 22. A catalyst system for the polymerizationof alpha-olefins comprising the catalyst component of claim 11 and anorganoaluminum cocatalyst.
 23. A catalyst component for thepolymerization of olefins obtained by (1) reacting (a) magnesiumdiethoxide with (b) trichlorosilane, (2) contacting the reaction productwith (c) ethylbenzoate, (3) contacting the product from (2) withtriethylaluminum, and (4) contacting the step (3) product with at leastone treatment of titanium tetrachloride.
 24. The catalyst component ofclaim 23 wherein the product from step (3) is contacted with titaniumtetrachloride two times.
 25. The catalyst component of claim 23 whereinone mol of component (a) is contacted with 0.5 to 10 mol component (b),the electron donor is used in an amount of 0.01 to 10 gram mol for 1gram atom of magnesium in the reaction product of step 1, theorganoaluminum compound is used in an amount of 0.1 to 20 mol per mol ofelectron donor compound and the titanium compound is used in the amountof more than 0.1 gram mol per 1 gram atom of magnesium in the contactproduct of step (3).
 26. The catalyst component of claim 25 wherein thetitanium compound is used in an amount of 1 to 50 gram mol per gram atomof magnesium.
 27. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 23 and an organoaluminumcocatalyst.
 28. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 24 and an organoaluminumcocatalyst.
 29. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 25 and an organoaluminumcocatalyst.
 30. A catalyst system for the polymerization of olefinscomprising the catalyst component of claim 26 and an organoaluminumcocatalyst.